New dyestuffs of the perylene tetracarboxylic acid series



United States Patent NEW DYESTUFFS OF THE PERYLENE TETRA- CARBOXYLICACID SERIES Wilhelm Eckert, Frankfurt am Main, and Hermann Remy, BadSoden (Taunus), Germany, assignors to Farhwerke HoechstAktiengesellschaft vormals Meister Lucius & Bruning, Frankfurt am Main,Germany, a corporation of Germany No Drawing. Application April 29, 1957Serial No. 655,538

larly it relates to dyestuffs corresponding to the following formula:

Cl (I31 wherein X represents a hydrogen or chlorine atom.

In our US. patent application Serial No. 661,261, filed May 23, 1957,now abandoned, for New Dyestutf of the Perylene Tetracarboxylic AcidSeries, is described a process for the manufacture of a dyestulf whichcan be i used with special advantage for coloring plastics, such aspolyvinyl chloride containing a plasticizer or polyethylene, lacquersand printing inks, which comprises condensingperylene-3,4,9,IO-tetracarboxylic acid or its anhydn'de withparacyclohexyl-aniline. The colored products are distinguished by verygood properties of fastness.

Now we have found that dyestuffs of similar excellent properties areobtained by reacting perylene-3,4,9,l0-tetracarboxylic acid or itsanhydride with 3-chloroaniline or 3,4-dichloroaniline.

The new dyestuffs are very suitable as pigments in the printing ink andlacquer industries, for fast coloring plastics, such as polyvinylchloride containing a plasticizer or polyethylene, furthermore forcoloring socalled bakable lacquers or for dyeing the spinning solution.

The following examples serve to illustrate the invention, but they arenot intended to limit it thereto, the parts being by weight unlessotherwise stated, and the relationship of parts by weight to parts byvolume being the same as that of the kilogram to the liter:

Example 1 20 parts of perylene-3,4,9,IO-tetracarboxylic aciddianhydride, 40 parts of 3-chloroaniline and 10 parts by volume ofconcentrated hydrochloric acid are introduced successively into 400parts by volume of quinoline, while stirring. The mixture is heated for15 hours at 200 C., while continuously distilling off the water. Theproduct is suction filtered in the cold, washed several times withmethanol, boiled with dilute sodium hydroxide solution, washed with hotwater until neutral, and dried.

The red dyestufl which crystallizes from quinoline in short prisms doesnot melt at a temperature up to 300 C., is diflicultly soluble in thecustomary organic solvents and dissolves in concentrated sulfuric acidto a violet solution without fluorescence. It is distinguished by anextraordinary brightness and excellent fastness properties, both inlacquers and in polyvinyl chloride mixtures, and possesses a very goodfastness to oil, to over-spraying, to solvents, to bleeding and tolight.

Patented Sept. 22, 1959 Example 2 20 parts ofperylene-3,4,9,IO-tetracarboxylic acid dianhydride, 48 parts of3,4-dichloroaniline and 10 parts by volume of concentrated hydrochloricacid are introduced successively into 400 parts by volume of quinoline,while stirring. The mixture is heated for 15 hours at 200 C., whilecontinuously distilling off the water. The product is suction-filteredin the cold, washed several times with methanol, boiled with dilutesodium hydroxide solution, washed with hot water until neutral, anddried.

The red dyestufi which is diflicultly soluble in the customary organicsolvents does not melt at a temperature up to 300 C. and dissolves inconcentrated sulfuric acid to a violet solution without fluorescence. Itis distinguished by an extraordinary brightness and excellent fastnessproperties, both in lacquers and in polyvinyl chloride mixtures, andpossesses a very good fastness to oil, to over-spraying, to solvents, tobleeding and to light.

Example 4 wherein X represents a member selected flom the groupconsisting of hydrogen and chlorine.

2. The dyestutf corresponding to the following formula 01 f 11 o 0 O 0 53. The dyestuif corresponding to the following formula 31 ff 11 oo H II0 0 References Cited in the file of this patent FOREIGN PATENTS 505,332Canada Aug. 24, 1954

1. THE DYESTUFFS CORRESPONDING TO THE FOLLOWING GENERAL FORMULA